N-(amino-1, 2, 4-triazolyl) itaconamides and polymers thereof



United States Patent N-(AMINO-LZA-TRTAZOLYL) ITACONAMIDES AND POLYMERS THEREOF Gaetano F. DAlelio, Pittsburgh, Pa., assignor to Koppers Company, Inc., a corporation of Delaware N0 Drawing. Application June 26, 1953 Serial No. 364,512

13 Claims. (Cl. 26078) This invention relates to new monomers and to new polymeric materials derived therefrom and is particularly directed to the polymerization products obtained by polymerizing a mass comprising as a new monomer an itaconic acid amide of a diamino-1,2,4-triazole in the presence or absence of other ethylenic copolymerizable compounds especially acrylonitrile. The invention also relates to compositions of these polymerization products adapted to the formation of shaped articles, in many cases to molecularly oriented shaped articles, particularly to fibers, threads, bristles, monofilaments, etc., hereinafter referred to as fibers, and other shaped articles such as films and the like, which articles show improved dyeing properties.

It has been known for some time that certain copolymers of acrylonitrile may be adapted to the preparation of shaped articles, such as, films, fibers, foils, tubes, etc. Some of these copolymers have been regarded as capable of being cold-drawn to produce structures molecularly oriented along the fiber axis. Cold-drawing may be defined as the stretching of a polymeric material at a temperature below the melting point of the material to give a molecularly oriented structure.

The resistance of acrylonitrile polymers to dyes of all types has presented serious dyeing problems, especially in the development of synthetic fibers from these polymers. In fact, in order to dye polyacrylonitrile one commercial process resorts to the use of high pressures with water solutions or organic dispersions of dyes. It has been proposed that improvement in dye susceptibility can be obtained by the use of itaconic acid in small amounts as copolymerizing monomer in the preparation of acrylonitrile polymers. However, the polymer products obtained thereby have a tendency to crosslink upon standing at temperatures of at least about 70-80 C. or upon spinning from hot solutions. Such crosslinking causes spoliation of material by gelation during storage, embrittlement of fibers, fouling of spinning jets, and other production diificulties.

In accordance with the present invention it has now been found that crosslinking can be avoided and that improvements in dyeing properties of acrylonitrile polymers are obtained by the polymerization of monomeric masses comprising acrylonitrile and an itaconic acid amide of a diamino-1,2,4-triazole with or without other copolymerizable ethylenic compounds. It has been found further that in addition to the fact that the itaconic acid amides of diarnino-1,2,4-triazole yield particularly valuable copolymers with acrylonitrile, they can also be used advantageously to form copolymers with other types of copolymerizable ethylenic compounds. It has been found still further that the itaconic acid amides of diamino-1,2,4- triazole can be polymerized per se to form useful polymers. Thus it has been found that valuable polymerization products may be prepared in accordance with the invention bypolymerizing a monomeric mass comprising an itaconic acid amide of a diamino-l,2,4-triazole either in the presence or absence of other ethylenic copolymerizable compounds such as acrylonitrile and the other copolymerizable ethylenic compounds listed hereinafter.-

The itaconic acid amides of diamino-1,2,4-triazoles are prepared by acylating guanazole (3,5-diamino-l,2,,4-tri-' azole) or a guanazole derivative with an itaconic acylat ing agent such as itaconic acid itself and various of its derivatives such as the anhydride, the acid chloride, the mono-esters, and the mono-amides. Since itaconic acid is a dibasic acid and guanazole is a difunctional base, various types of amides can be obtained. Thus by react ing one mol of itaconic acid with one mol of guanazole, there is obtained the mono-amide acid of guanazole and itaconic acid which has the formula H N-AHNHCOBCOOH in which A is the 1,2,4-triazole nucleus of guana'zole and B is the C-CH group of itaconic acid. This acid can then be esterified to give an ester of the mono-amide acid of guanazole and itaconic acid which has the formula or further amidated with ammonia or another amine to give an amide of mono-amide acid of guanazole and itaconic acid which has the formula These types of compounds can also be formed by using the appropriate monoester or mono-amide of itaconic acid to acylate the guanazole. By reacting two moles of guanazole with one mol of itaconic acid there is obtained the di-(mono-amide) of guanazole and itaconic acid which has the formula Also by reacting one mole of guanazole with two moles of itaconic acid there is obtained the diamide-diacid of guanazole and itaconic acid which has the formula This dibasic acid can then be esterified or further amidated to give the monoor diesters or the monoor diamides thereof. These di-itaconic derivatives advantageously are avoided except where crosslinking is not objectionable.

For reasons of economy and ease of preparation, the methyl or ethyl esters of the mono-amide acid of guanazole and itaconic acid are usually preferred when an ester is used. These are prepared by reacting molar proportions of itaconic acid chloride or anhydride with guanazole to form the mono-amide acid of guanazole and itaconic acid. The acid chloride and anhydride are sufficiently reactive to form the amide merely upon mixing at room temperature. In some cases where anhydride or acid chloride are not as reactive or in order to get more complete action gentle heating may be advantageous. This acid can be converted readily to the sodium or potassium salt and esterified at room temperature with dimethyl sulfate or diethyl sulfate to form the methyl or ethyl ester. Alternatively, itaconic acid is methylated or ethylated to the mono stage by refluxing it with methanol or ethanol in the presence of a small amount of an esterification catalyst, such as sulfuric acid, toluene sulfonic acid, cation-exchange resins containing sulfonic acid groups, etc. The monoester thus formed is then converted to the acid chloride by refluxing with thionyl chloride, and the acid chloride is reacted with guanazole to form the desired methyl or ethyl ester of the' mono-itaconic mono-amide acid of guanazole.

Guanazole is readily prepared by refluxing an aqueous 3 solution of dicyandiamide and a hydrazine salt, such as, the hydrochloride and then neutralizing the acid. Substituted guanazoles can be prepared in which one or more of the hydrogens are replaced by alkyl, aryl, aralkyl, alkaryl, and cycloaliphatic groups or in which one of the hydrogens is replaced by an acyl group, as listed below, by using a substituted hydrazine instead of hydrazine and/or a substituted biguanide instead of dicyandiamide, and/or by monoacylating the guanazole before or after the acylation with the itaconic acid.

The itaconic acid amides of diamino-l,2,4-triazoles can be represented by the general formula in which Y is either the radica1GR'R" or the radicals RO- or R N- in which R is hydrogen or an alkyl, aryl,

aralkyl, alkaryl, or cycloaliphatic group which may have halogen-, acyloxy-, or alkoxy-substituents or when Y is R N-, the Rs may be linked together to form with the nitrogen a heterocyclic group; G is a diamino-l,2,4-triaz olegroup (the guanazole nucleus); R is hydrogen, the

Thus in the amides of the invention one or more of the hydrogens of guanazole can be replaced by such groups as methyl, ethyl, isopropyl, n-butyl, sec-butyl, amyl, hexyl, decyl, phenyl, tolyl, xylyl, benzyl, phenethyl, naphthyl, cyclohexyl, cyclopentyl, and the like and one of thehydrogens can be replaced by an acyl group such as acetyl, formyl, propionyl, butyryl, benzoyl, etc. Advantageously, the hydrocarbon substituents should contain not more than a total of four carbon atoms and advantageously should not contain more than two carbon atoms each. The acyl substituents advantageously are the acyl groups of saturated monocarboxylic acids (alkanoyl) preferably the formyl and acetyl groups.

When the amides used in the practice of the invention contain an ester group or an amide group othe than group G'R" the radical R may be methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, amyl, hexyl, decyl, chloromethyl, chloroethyl, cyclohexyl, methyl-cyclopentyl, propyl-cyclopentyl, amyl-cyclopentyl, methyl-cyclohexyl, dimethyl-cyclohexyl, chlorocyclohexyl, phenyl, chlorophenyl, Xenyl, naphthyl, tolyl, chlorotolyl, Xylyl, ethyl-phenyl, propyl-phenyl, isnpropyl-phenyl, benzyl, chlorobenzyl, phenethyl, phenyl-propyl, phenyl-butyl, acetoXy-ethyl, chlorophenoXy-ethyl, acetoxy-propyl, acetoxy-isopropyl,

acetoxy-phenyl, acetoXy-benzyl, acetoXy-tolyl, acetoXycyclohexyl, methoxy-propyl, ethoxy-propyl, methoxyphenyl, methoxy-benzyl, methoxy-tolyl, methoxy-cyclohexyl, etc. or part of a heterocyclic amino group, such as, the piperidyl, piperazino and morpholine groups.

As an illustration the itaconic ester amides of guanazole itself (and their corresponding polymer units) can be represented by the following formulas:

wherein R is as defined above, advantageously methyl or ethyl.

The proportions of the amide in the polymerization products of the invention can vary over a wide range, ranging from all or substantially all amide down to very small amounts of amide such as may be employed in acrylom'trile polymers to impart dye susceptibility thereto. Although even smaller amounts are somewhat effective, the improvement in susceptibility of acrylonitrile copolymers to dyes becomes particularly noticeable when the amide content of the copolymer is about 0.1 percent and the susceptibility increases as the amounts of amideis increased. Ordinarily suflicient improvement in dye susceptibility is obtained with amounts of amide ranging up to about 10 or 15 percent but it may be advantageous for reasons such as in the preparation of ion-exchange polymers or additives to improve dyeing properties to V have a major proportion of amide in the acrylonitrile copolymer. In such cases the concentration of amide may range up to or approaching percent. Within these proportions acrylonitrile copolymers of the invention show great 'afiinity toward many dyes especially basic, acidic, vat, and cellulose acetate dyes.

In addition to the improvements eifected in the resulting copolymers, the use of itaconic acid amides of diamino-l,2,4-tn'azoles has certain other advantages over the use of the corresponding acids. For example, the amides are more soluble in acrylonitrile than the acids. Therefore it is generally easier to get complete copolymerization of the amide with acrylonitrile in solution, emulsion and suspension polymerizations. Still further advantages accrue from the presence of these amides. Thus when non-esterified monoamides are used the copolymers of the invention show high susceptibility to basic dyes.

The acrylonitrile copolymers discussed herein are soluble in N,N-dimethyl acetamide (DMA), N,N-dimethyl formamide (DMF), butyrolactone, ethylene carbonate, N,N-dimethyl methyl urethane of the formula (CH NCOOCH ethylene carbamate, N-methyl-Z-pyrrolidone, and a number of similar solvents, used alone or in conjunction with N,N-dimethyl cyanamide, N,N-dimethyl cyano acetamide, N,N dimethyl methoxy acetamide, methylene dinitrile, methylene dithiocyanate, formyl caprolactam, formyl morpholine, tetramethylene sulfone, etc. Nitroalkaues, such as nitromethane, may be used as solvents for such copolymers having no more than about 85 percent acrylonitrile, providing the comonomers used in preparing such copolymers do not have substituent groups of equal or greater secondary bonding force than the cyano groups in acrylonitrilee. Copolymers of the present invention which have high proportions of monomers of relatively low secondary-valence bonding strength, such as, vinyl chloride, may often be dissolved in acetone or mixtures of acetone and solvents of the above types.

This invention will be more fully described by the following examples' which illustrate methods of practicing the invention. In these examples and throughout the specification, parts and percentages are intended to mean parts by Weight and percentages by weight.

Example I 20.2 grams (0.2 mol) guanazole is admixed with approximately ml. diethyl ether and there is added slowly and with stirring 22.4 grams (0.2 mol) itaconic anhydride. The mixture is refluxed for approximately /z hour, cooled and the ether evaporated. The residue is recrystallized from absolute ethanol. the mono-acid amide of guanazole and itaconic acid.

Ultimate analyses for carbon, hydrogen and nitrogen and molecular weight determinations on the product give results which are in close agreement with the theoretical values for the mono-acid amide of guanazole and itaconic acid.

Substitution of equivalent quantities of diamino-1,2,4- triazoles in the foregoing procedure for the guanazole there used yields the various mono-amides of itaconic acid and guanazoles of this invention which are characterized by ultimate analyses and molecular weight determinations as in the foregoing procedure.

Example II 42.6 grams (0.2 mol) mono-acid amide of guanazole and itaconic acid (prepared as in Example I) is dissolved in a minimum amount of water and 8.0 grams (0.2 mol) sodium hydroxide added slowly to form the sodium salt. The water is evaporated and the residue is admixed with approximately 150 ml diethylether. There is added slowly and with stirring 25.0 grams (0.2 mol) dimethyl sulfate. The ether is evaporated and the residue recrystallized from absolute ethanol. There is obtained the methyl ester of the mono-amide of itaconic acid.

Ultimate analyses for carbon, hydrogen and nitrogen and molecular weight determinations on the product give results which are in close agreement with the theoretical values for the methyl ester of mono-acid amide of guanazole and itaconic acid.

Substitution of the various mono-amides of Example I or diethyl sulfate respectively in the foregoing procedure for the mono-acid amide of guanazole and itaconic acid and the dimethyl sulfate there used yields the various methyl and ethyl esters of the mono-amides of itaconic acid of this invention which are characterized by ultimate analyses and molecular weight determinations as in the foregoing procedure.

Example 111 42.6 grams (0.2 mol) mono-acid amide of guanazole and itaconic acid is admixed with approximately 150 ml. diethyl ether and 29.7 grams (0.25 mol) thionyl chloride and the mixture refluxed for approximately one-half hour. The ether is evaporated and there is obtained the acid chloride.

This acid chloride is added slowly and with stirring to a mixture of 10.0 grams (0.2 mol) dimethyl amine and 150 ml. diethyl ether in a flask equipped with a reflux condenser. After the addition of the acid chloride the mixture is refluxed for approximately /2 hour and the ether is then evaporated. The residue is dissolved in water and shaken with 29.0 grams (0.125 mol) silver oxide to remove the chloride ion. The mixture is filtered and the filtrate evaporated to dryness. The residue is recrystallized from absolute ethanol. There is obtained N-dimethyl-N'-(amino 1,2,4 triazolyl) itaconic acid diamide.

Ultimate analyses for carbon, hydrogen, and nitrogen and molecular weight determinations on the product give results which are in close agreement with the theoretical values for N-dimethyl-N-(amino-1,2,4-triazolyl)-itaconic acid diamide.

Substitution of equivalent quantities of the various mono amides of Example I or dialkyl amines, respectively, in the foregoing procedure for the mono-acid amine of guanazole and itaconic acid yields the various unsymmetrical diamides of this invention which are characterized by ultimate analyses and molecular weight determinavtions as in the foregoing procedure.

There is obtained Example IV 46.3 grams (0.2 mol) of the acid chloride of Example III is added slowly and with stirring to a mixture of 20.2 grams (0.2 mol) guanazole and 150 ml. diethyl ether in a flask equipped with a reflux condenser. After addition of the acid chloride, the mixture is refluxed for approximately /2 hour and the ether is then evaporated. The residue is dissolved in water and shaken with 29.0 grams (0.125 mol) silver oxide to remove the chloride ion. The mixture is filtered and the filtrate evaporated to dryness. The residue is recrystallized from absolute ethanol. There is obtained N,N-(amino-1,2,4-triazolyl)-itaconic acid diamide.

Ultimate analyses for carbon, hydrogen and nitrogen and molecular weight determinations give results which are in close agreement with the theoretical values for N,N'-(amino-1,2,4-triazolyl)-itaconic acid diamide.

Substitution of equivalent quantities of the various acid chlorides obtained as in Example III or various diamino- 1,2,4-triazoles in the foregoing procedure for the particular acid chloride and guanazole there used yields the various diamides of ethenedioic acids of this invention which are characterized by ultimate analyses and molecular weight determinations as in the foregoing procedure.

Example V Five' polymers of acrylonitrile are prepared from the following monomer compositions:

The mono- Acrylonitrile, amide acid of Polymer parts guanazole and itaconic acid,

parts parts of monomer or monomer mixture is, in each case, slowly added over a period of less than an hour to 750-l,000 parts of distilled water at 3050 C. containing dissolved therein one part of ammonium persulfate, 0.6 to 1.5 parts or" sodium bisulfite and 0.5 part of sodium dodecylbenzene sulfonate. The reaction is continued for 2-6 hours, at which time a yield of about 90 percent solid polymer is precipitated. The resulting polymers have molecular weights over 10,000. Each polymer is dissolved in N,N-dimethyl acetamide or butyrolactone and a film cast from each solution.

A water solution of methylene blue dye (a basic dye) is prepared by making a paste of the dye with one percent by weight dye solution. This dye solution is kept boiling for one hour while the aforementioned films are immersed therein for one hour. The dyed films are then removed and separately subjected to washing with boiling water for one hour, the boiling water being changed frequently to remove the desorbed dye. The unmodified polyacrylonitrile film when treated in this manner shows only a light tint, Whereas the amide copolymers are dyed a deep and dense shade. Identical films, cold-drawn and heat-treated, show dyeing characteristics similar to the undrawn films.

Fibers are spun from the same N,N-dimeihyl acetamidc or butyrolactone solutions either by dry spinning or by wet spinning, into glycerine baths. The fibers are substantially freed from solvent and dried. After cold-drawing the dried fibers 600900 percent at 145' C. and subsequently heat-treating them at C. for one hour, the fibers are given the same dyeing and Washing treatment described above with the same results as for the films a light tint being acquired by the unmodified polyacrylonitrile fibers and a deep and dense color being given to the itaccuatc copolymer fibers.

Example VI Five polymers of acrylonitrile are prepared from the following monomer compositions:

To 900 parts of water, adjusted to a pH of about three, in a suitable reactor, is added 0.5 to 1 part sodium dodecylbenzene sulfonate, 1.0 part of ammonium persulfate, 0.5 part of sodium bisulfite, and 100 parts of monomer or monomer mixture. The reactor is then flushed with deoxygenated nitrogen and heated with agitation to 50 C. for 24 hours. Steam is introduced into the reactor to remove unpolymerized monomers from the mixture. A small amount of aluminum sulfate is added to the mixture and the polymer isolated by filtration.

The polymer is then washed with Water and with methyl alcohol. A portion of the polymer is dissolved in dimethyl formamide or butyrolactone and a film cast from the solution. The film is washed entirely 'free of solvent and stretched at a ratio of about 8:1 in a glycerine bath at 135 to 145 C. The film is then washed in water and dyed in a bath containing for each part of film 0.05 part of l,5-diamino-4,8-dihydroxyanthraquinone-3-sulfonic acid, 0.03 part sulfuric acid and 50 parts water (50:1 bath-fiber) ratio at boiling temperature for one hour. The film is then removed and washed with water and scoured for 15 minutes in a 0.4 percent soap solution at 85 C. Whereas the unmodified polyacrylonitrile when treated in this manner had little or no color, all of the copolymers are dyed to a deeper blue shade.

Fibers are spun from the same solutions either by dry spinning, or by wet spinning. The fibers are substantially freed from solvent and dried. After cold-drawing the dried fibers 600-900 percent at l20145 C. and subsequently heat-treating them at 150 C. for one hour, the fibers are given the same dyeing and washing treatment described above with the same results as for the films, alight tint being acquired by the unmodified polyacrylonitrile fibers and a deep and dense color being given to the copolymer fibers. The polymers of this example are also soluble in dimethyl formamide, dimethyl acetamide, tetramethyl urea, butyrolacetone, ethylene carbonate, formyl morpholine, etc,

Instead of the methyl ester of the above example, various other esters can be used, such as the ethyl, propyl, isopropyl, butyl, 'isobutyl, tertiary-butyl, hexyl, tolyl, phenyl, naphthyl, cyclopentyl, cyclohexyl, benzyl, phenethyl, etc. esters. Likewise, the esters of the other monoamideacids disclosed above can-be used. The procedure of this example can also be used with monoand diesters of diamide-diacids as disclosed above.

Example VII 7 Five parts of the copolymer fiber D of Example V is dyed to a deep green shade using the vat color dimethoxydibenzanthrone at 70 C. in a bath containing 0.5 part of dye, 0.25 part sodium hydroxide, 0.5 part sodium hydrosulfite and 100 parts of water (20:1 bath-fiber ratio). After the first 15 minutes of heat, 0.25 part of Glaubers salt is added. The sample is then oxidized in a 0.5 percent sodium dichromate 1.0 percent acetic acid at 70 C. for .30 minutes in a 20:1 bath-fiber ratio. The dyed fiber is then secured in a 0.5 percent boiling soap solution. A sample of yarn prepared from the unmodified polyacrylonitrile and dyed under the same conditions resulted in alight shade of color.

When 1,5 di p anisoylamino 4,8 dihydroxyanthraquinone is used as the vat dye, the copolymer fiber is dyed a strong violet color.

The procedures of this example and of Example V can be used with the various other itaoonic amide-acids of diamino-1,2,4-triazoles disclosed above instead of the monoamide-acid of guanazole and itaconic acid.

Example VIII The'procedure of Example V is repeated for the polymerization of the following monomer compositions:

Methyl ester Aerylo- Vinyl of the mono- I-olymer nitrile, Chloride, amide-acid Copolymer Soluble parts parts or guanazole in and itaconic acid parts 92 5 3 DMF, DMA, etc. S7 10 3 DMF, DMA, etc. 82 3 DMF, DMA, etc. 77 2O 3 NOzMc. 57 3 NOzMc. 37 3 Acetone.

Sometimes copolymers D and E, when dissolved in nitrornethane may have gelled, partially dissolved particles known as fisheyes. in such cases, the solubility can be improved by the addition of small amounts of materials which are good solvents for acrylonitrile polymers, such as butyrolactone, ethylene carbonate, dimethyl formamide, dimethyl acetam-ide, tetramethyl urea, etc. In addition, certain materials which are relatively poor solvents for polyacrylonitrile, such as diethyl 'formamide, diethyl acetamide, diethyl propionamide, etc., can be added to improve the solubility. Also, when acetone solutions of copolymer F contain gelled particles, clarification of the solution can be effected by the addition of nitromethane, diethyl formamide, diethyl acetamide, etc.

Dyeing tests of these copolymers show improvements in dyeing susceptibility similar to those of Example V.

Example IX The procedure of Example V is repeated for the polymerization of the following monomer compositions:

Dyeing tests of these co'polymers show improvements in dye susceptibility similar to Example V. In place of 60 styrene, various styrene derivatives can be used, such as alyha-methyl-styrene; nuclear-substituted chloro-styrenes,

i. e., ortho-, meta-, and para-chloro-styrenes, dichlorostyrenes, for example,.the 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, and

such as ortho-,, .meta-, and par'a-cyano-styrenes, dicyanostyrenes, nuclear substituted alkyl-styrenes, such as monoand di-methyl-styrenes, monomonand di-isopropyl-styrenes, aryl-substituted styrenes, i. e., para-.phenyl-styrene, etc.; cycloaliphaticsubstituted such as ortho-, meta-, para-fluoro-styrene, .difluoro-styrenes, etc.; trifiuoro-methyl-styrenes, such as ortho-, meta-, and para-trifiuoromethyl-styrenes, di-(trifiuoromethyl)-styrenes, and 'various other styrenes or mixtures of any number of these with eachother-or with styrene.

3,5-dichlorowstyrenes; trichloro-styrenes; cyano-styrenes,

and di-ethyl-styrenes,

styrenes, such as .para-cyclohexyl-styrene; fluoro-styrenes,

9 Example X The procedure of Example V is repeated for the polymerization of the following monomer compositions:

Methyl ester of the monoamideacid of guanazole and itaconic acid parts vinylidene Chloride, parts Acrylonitrile, parts copolymer Soluble Polymer m- DMF, DMA, etc. DMF, DMA, etc. DMF, DMA. etc. DMF, DMA, etc. DMF, DMA, etc.

homo 018010101 With the above vinylidene chloride copolymers and similar copolymers having a total of acrylonitrile and vinylidene chloride of at least 85 percent in the polymer molecules, only the more active solvents, such as butyrolactone, N.N-dimethyl acetamide, N.N-dimethyl formamide, N,N,N,N'-tetramethyl urea, etc, can be used as solvents. The above copolymers dye more readily and throughly than similar coplymers containing no amide.

Example XI The procedure of Example V is repeated for the polymerization of the following monomer compositions:

Ethyl ester of Aerylovinylidene Vinyl monoamide- Polymer nitrile, Chloride, Chloride, acid of parts parts parts guanazole and itaeonic acid, parts The dyeing tests of the copolymer products show dye susceptibility similar to the copolymers of Example V.

The procedures of Example VIII, IX and X and the example given below may be used with the various other Example XII Polymeric monoamide-acid of guanazole and itaconic acid is prepared substantially in accordance with the procedure of Example V. A 10 percent solution of this polymer is prepared in dimethyl formamide and added to a dimethyl formamide solution of polyacrylonitrile, containing 20 percent polymer, so that a composition consisting of 90 parts of polyacrylonitrile and 10 parts of the amide is obtained. The solution is heated to 130 C. after which the solution is filtered. Films and fibers prepared from this mixture are dyed in accordance with the process of Example V, and satisfactorily dyed, shaped articles are obtained. The unmodified polyacrylonitrile without the addition of the amide showed little or no dye retention.

Instead of using a homopolymers, copolymers of the amide, such as polymers D and E of Example VI, may be used as modifiers for the unmodified homopolymers of acrylonitrile. For example, polymer E of Example VI, which consists of 80 parts of acrylonitrile and 20 parts .of the methyl ester of the monoamidc-acid of guanazole 10 and itaconic acid has excellent compatibility with homopolymers of acrylonitrile. In many cases, it is desirable to use the copolymers of the amide which have even a higher ratio of the amide, as for example, 50 to parts of the amide copolymerized with acrylonitrile or methacrylonitrile. In other cases, the copolymers of the amide with other monomers are satisfactory such as, for ex ample, copolymers of styrene, vinyl chloride, vinylidene chloride, alpha-methyl-styrene, etc.

When it is desired to modify an acrylonitrile copolymer such as the copolymer of acrylonitrile and styrene or the copolymers of acrylonitrile and other copolymerizable ethylenic compounds, it is usually desirable to use as modifiers copolymers containing at least one structural unit present in the acrylonitrile copolymer. Thus as there are present in the acrylonitrile copolymer, structural units derived from the acrylonitrile and styrene, it is desirable to have present in the modifying copolymer structural units derived from styrene and/or acrylonitrile, advantageously both, in addition to those derived from the amide. By thus including in the modifying copolymers structural units of the same type as the structural units of the copolymer to be modified, greater compatibility between the acrylonitrile copolymer to be modified and the modifying copolymer is obtained and the two are more readily soluble in the mutual solvent and will more readily mix into homogeneous polymer mixtures.

The polymerization products of the present invention have in the polymer molecule a plurality of repeating units of the formula in which Y, G, R and R are as indicated above and will contain additional repeating units of the formula when the amide iscopolymerized with acrylonitrile.

In addition, the polymerization products can contain any number of repeating units of the type obtained by the copolymerization of an itaconic acid amide of a diamino- 1,2,4-triazole or a mixture of this amide and acrylonitrile with one or more copolymerizable ethylenic compounds, such as, for example, vinylidene chloride, vinyl chloride, styrene, alpha-methyl-styrene, methacrylonitrile, fumaronitrile, beta-cyano-acrylamide and methyl beta-cyanoacrylate.

As previously indicated, the solvent resistance of such copolymers as contain one or more monomer units in addition to those formed by the acrylonitrile and the amides of the invention is affected by the type and proportion of copolymerizing monomer or monomers used to replace part of the acrylonitrile. For example, copolymers containing small amounts of the amide units can containvarious proportions of such monomer units as obtained from vinylidene chloride, methacrylonitrile, fumaronitrile, and beta-cyano-acrylamide without considerable reduction in solvent resistance. Replacement of acrylonitrile units in the copolymers by vinyl chloride, styrene and alpha-methyl-styrene units result in copolymers of lowered solvent resistance, the amount of such lowering in resistance in each case depending on the amount substituted. In addition to the solvent resistance, certain other physical properties of the copolymers are affected by the presence of these additional units in the copolymers. The amount and character of the changes in physical properties of these copolymers depend again on the type and proportion of copolymerizing monomer or monomers used. For example, the tensile strength of an acrylonitrile-amide type copolymer will decrease much more when a monomer having relatively weak secondary bonding forces, such as styrene or ethylene is used to replace part of the acrylonitrile than when one or more monomers having relatively strong bonding forces, such as methacrylonitrile, fumaronitrile, beta-cyano-acrylamide, methyl beta-cyano-a'crylate and vinylidine chloride, is used to replace part of the acrylonitrile. Moreover, the ability of these copolymers to form molecularly oriented shaped articles depends on the type and amount of the copolymerizing monomer or monomersused to replace acrylonitrile.

Other copolymerizable ethylenic compounds, which can also be present in the polymerizable masses for copolymerization with the amides used in the practice of this invention include one or more of the following: acrylates, e. g. methyl acrylate; methacrylates, e. g. methyl methacrylate; acrylamides; methacrylamides; vinyl esters, such as vinyl-acetate; maleates, such as dimethyl and diethyl maleates; fumarates, such as dimethyl and diethyl furnarates; itaconic diesters, such as dimethyl and diethyl itaconates; itaconamide; vinyl halides, such as vinyl fluoride, vinylidine fluoride, tetrafluoroethylene, trifluorochloroethylene; vinyl aryls, such as vinyl naphthalenes and substituted styrenes as listed in Example IX, etc.

The polymerization products of this invention can be prepared by various polymerization systems, such as emulsion, suspension, mass and solution polymerizations. In addition to the monomers, the polymerizable mass can also contain other materials such as catalysts, e. g. peroxides, such as benzoyl peroxide, naphthyl peroxides, phthalyl peroxide, tertiary-butyl hydro-peroxide, hydrogen peroxide, cyclohexyl hydroperoxide, tertiary-butyl perbenzoate, etc., azo catalysts, persulfates, such as ammoni um persulfate, etc., solvents, suspension or emulsion media, emulsifying agents, suspension agents, plasticizers, lubricants, etc.

For use in the preparation of shaped articles, the polymerization products of this invention have molecular weights preferably of at least about 10,000. However, polymerization products of molecular weights less than 10,000 may be used for other purposes, such as impregnants, solvent resistant coatings, etc. The molecular weight of the polymerization products is dependent on the concentrations of the monomers, the amount and type of catalyst, the temperature of reaction, etc.

As is quite generally known in the field of high polymers, molecular orientation is usually indicated and identified by birefringence of polarized light, as under Nicol prisms, by increased density as compared to the density of the same polymer unoriented, and by characteristic X-ray diffraction patterns. When a material is crystalline or oriented, its X-ray diagram shows bright areas or spots for points of crystallization and dark areas for the non-crystalline regions. The intensity or number of these bright spots increases with the degree of orientation or crystallization. Amorphous or non-crystalline materials give X-ray diagrams havingvery few high lights or bright spots whereas crystalline or oriented materials give definite X-ray difiFraction patterns. In these patterns there are definite relationships of the bright spots with regard to position and spacing which are generally characteristic of the composition of the material being X- rayed. In fibers or films the orientation usually follows the direction of drawing or stretching so that the orientation is parallel to the fiber axis or a major surface.

Useful fibers can be made from the solutions of the copolymers of this invention by dry spinning, as in the preparation of cellulose acetate fibers, or by wet spinning, as in the preparation of viscose rayon. In Wet spinning, the solution of copolymer can be spun into a substance which is a non-solvent for the copolymer, but which is advantageously compatible with the solvent in which the copolymer is dissolved. For example, water, acetone, methyl alcohol, carbon disulfide, glycerine, chloroform, carbon tetrachloride, benzene, etc., can be used as a precipitating bath for N,N-dimethyl acetamide,-N,N,N, N'tetramethyl urea, butyrolactone, ethylene carbonate,

and other solvent compositions of these copolymers. The;

12 extruded fibers, from which substantially all of the solvent has been removed in the spinning step, about 1-10 percent remaining in the shaped article, can then be cold-drawn about l00900 percent preferably about 300-600 percent; and the drawn fiber heat-treat, usually at substantially constant length, at about IOU-160 C. to effect further crystallization and removal of the remaining solvent. The term heat-treated, as used herein,

refers to the application of heat to an object, usually 7 at a controlled temperature and usually by means of the medium surrounding the object.

Many of the acrylonitrile copolymers of this invention can be molecularly oriented, especially if there is no more than 15 percent of amide in the copolymer molecule.

This is true when the major portion of the copolymeris acrylonitrile, for example, percent or more acrylonitrile, or when the other copolymerizing monomers used in making such copolymers have substituent groups having secondary-valence bonding forces equal to or greater than exhibited by the cyano group in acrylonitrile. For example, if such monomers as methacrylonitrile, fumaronitrile, vinylidene chloride, beta-cyano-acrylamide and methyl beta-cyano-acrylate are used with acrylonitrile and an amide according to the invention, the proportion of acrylonitrile in the copolymers may be much less than 85 percent without destroying the capacity of molecular orientation. Molecularly oriented, cold-drawn,

shaped articles of particular usefulness are prepared from The polymerization products of this invention show great alfinity for the acetate, basic, acidic and vat dyes.

The cellulose acetate dyes which are elfective with these polymerization products are mainly aminoanthraquinone derivatives. The basic dyestuffs toward which these poly-' merization products show great aifinity are preferably those which contain amide, alkylamido, or ammonium groups, such as -NH N(CH3)2 N(C H NHC H N{CH OH, etc. and which may also be used in the form of their salts, i. e. the hydrochlorides, sulfates or oxalates. Some of these basic dyes are Methylene Blue, Rhodamine B, Indamine Blue, Auramine, Meldolas Blue, Chrysoidine Y, Acridine Yellow,

'Magneta, Crystal Violet, Thioflavine T, Saliranine and Bismarck Brown. The cellulose acetate dyes which are eilective with these polymerization products are mainly amino-anthraquinone derivatives, basic azo compounds and other baic substances, such as the Duranol, Dispersol, Sericol, etc. dyestuffs. A number of other acidic dyes that can be used are anthranilic acid 1-(4-sulfophenyl), 3-methyl-5-pyrazolone; l,5-diamino-4,8-dihydroxyanthraquinone-3-sulfonic acid; l-amino-naphthalene-4-sulfonic acid alpha-naphthol-4-sufonic acid; the sodium salt of sulfanilic acid aniline 2-benxoylamino-5-naphthol-7-sulfonic acid; the sodium salt of 4, 4-diaminostilbene-2,2-di-sulfonic acid :3 (phenoD ethylated; 1,5 diamino-4,8-dihydroxyanthraquinone-3- sulfonic acid; dye prepared by diazotizing l-aminonaphthalene-4-sulfonic acid and coupled with alpha-naphtol- 4-sulfonic acid; the sodium salt of (m-aminobenzoic acid o-anisidene) phosgenated; the sodium salt of (2- naphthol-6,8-disulfonic acid benzidine phenol) ethylated; dimethoxy dibenzanthrone; and 1,5 di panisoylamino-4,S-dihydroxyanthraquinone.

From the molecularly orientable copolymers of this invention fibers can be prepared having improved dyeing in which Y is selected from the class consisting of the carbonylophilic radicals piperidyl, piperazino, morpholino, RO, R N-, and

R is selected from the class consisting of hydrogen and the alkyl, aryl, aralkyl, alkaryl, and cycloaliphatic hydrocarbon groups and their halo-, carboxylic acy1oxy-, and alkoxy-derivatives; R is selected from the class consisting of hydrogen, carboxylic acyl, and alkyl groups; R" is selected from the class consisting of hydrogen and alkyl groups and in which R and R" contain together not more than four carbon atoms.

2. As a new monomeric compound an N-(amino-l,2,4- triozolyD-itaconamide having the formula 3. A polymer of the polymerizable monomer of claim 1.

4. The polymeric composition of claim 3 which contains in the polymer molecule a plurality of repeating units of the formula 5. A polymeric composition comprising a copolymer of acrylonitrile and an amide of itaconic acid and a diamino-1,2,4-triazole, said copolymer having a molecular weight of at least about 10,000 and containing in the polymer molecule no more than about 15 percent by weight of said amide.

6. The copolymer of claim 5 in which the diaminol,2,4-triazole is guanazole.

7. A cold-drawn fiber having molecular orientation and dye susceptibility to acid dyes, said fiber comprising a copolymer of acrylonitrile and an amide of itaconic acid and a diamino-1,2,4 -triazole, said copolymer having a molecular weight of at least about 10,000 and containing in the polymer molecule no more than about 15 percent by weight of said amide.

8. A cold-drawn fiber having molecular orientation and dye susceptibility to acid dyes, said fiber comprising a copolymer of about 60-989 percent by Weight acrylonitrile, about 0.1 to 5 percent of an amide of itaconic acid and a diamino-1,2,4-triazole, and about 1 to 39.9 percent by weight of a compound selected from the class consisting of vinyl chloride, vinylidene chloride, styrene, alpha-' 9. A cold drawn fiber having molecular orientation and dye susceptibility to acid dyes, said fiber comprising a copolymer of about 60-989 percent by weight acrylonitrile, about 0.1 to 5 percent by weight of an amide of itaconic acid and a diamino-1,2,4-triazole, and about 1 to 39.9 percent by Weight vinylidene chloride.

10. A cold-drawn fiber having molecular orientation and dye susceptibility to acid dyes, said fiber comprising a copolymer of about 60-989 percent by weight acrylonitrile, about 0.1 to 5 percent by weight of an amide of itaconic acid and a diamino-1,2,4-triazole, and about 1 to 39.9 percent by Weight vinyl chloride.

11. A cold-drawn fiber having molecular orientation and dye susceptibility to acid dyes, said fiber comprising a copolymer of about 60-989 percent by weight acrylonitrile, about 0.1 to 5 percent by weight of an amide of itaconic acid and a diamino-1,2,4-triazole, and about 1 to 39.9 percent by weight styrene.

12. A cold-drawn fiber having molecular orientation and dye susceptibility to acid dyes, said fiber comprising a copolymer of about to 98.9 percent by weight acrylonitrile, about 0.1 to 5 percent by weight of an amide of itaconic acid and a diamino-1,2,4-triazole, and about 1 to 39.9 percent by Weight of a compound selected from the class consisting of vinyl chloride, vinylidene chloride, styrene, alpha-methyl-styrene, methacrylonitrile, fumaronitrile, beta-cyano-acrylamide, and methyl beta-cyano acrylate.

13. The cold-drawn fiber of claim 12 in which the diamino-l,2,4-triazole is guanazole.

References Cited in the file of this patent UNITED STATES PATENTS 2,643,990 Ham June 30, 1953 

1. A NEW MONOMERIC COMPOUND HAVING THE FORMULA 